Belt

ABSTRACT

In the belt according to the present invention, the whole or a part of a belt body is formed from a thermoplastic resin composition (C) comprising a thermoplastic resin W and a modified ethylene copolymer (B) dispersed and contained. therein. The modified ethylene copolymer (B) is preferably a copolymer, modified with an unsaturated carboxylic acid or a derivative thereof, of ethylene with at least one monomer component selected from (i) olefin components except for ethylene, (ii) diene components and (iii) ester components having an ethylenically unsaturated group. The belt according to the present invention hardly causes abrasion, damage, cracks, breakage and the like on the belt body and is remarkably excellent in durability, even if the belt is used at a high load for a long time.

CROSS REFERENCE TO RELATED APPLICATIONS

This application a Divisional of copending application Ser. No.14/007,818, filed on Sep. 26, 2013, which was filed as PCI InternationalApplication No. PCT/JP2012/059281 on Mar. 29, 2012, which claims thebenefit under 35 U.S.C. §119(a) to Patent Application No. 2011-081232,filed in Japan on Mar. 31, 2011, all of which are hereby expresslyincorporated by reference into the present application.

TECHNICAL FIELD

The present invention relates to a belt (excluding toothed belts)utilized for power transmission, conveyance and the like, particularlyto a belt in which the whole or a part of a belt body is formed from aspecific thermoplastic resin composition.

BACKGROUND ART

Conveyance belts and transmission belts require bending fatigueresistance, abrasion resistance, heat resistance, durability and thelike, for example, as flat belts, V-belts and the like. Belts areusually imparted with a tension and used in an elongated state. Beltsare used in combination with resin-made or metal-made pulleys rotatingat a high speed, and are contacted with pulleys, and caused to be woundtherearound and to be rubbed together, and are exposed to collision withand rubbing on conveyed materials, and the like.

Japanese Patent Laid-Open Nos. 2009-197896 and 2011-121689 discloseconveyance flat belts whose belt body is formed from a thermoplasticelastomer such as a thermoplastic polyurethane elastomer.

However, if conventional flat belts and V-belts having a belt bodythereof formed from a thermoplastic elastomer such as a thermoplasticpolyurethane elastomer are used as high-load power transmission belts,the belt body abrades and cracks in an early stage, and provides thebelts with insufficient durability in some cases.

CITATION LIST Patent Literature

Patent Literature 1: Japanese Patent Laid-Open No. 2009-197896

Patent Literature 2: Japanese Patent Laid-Open No. 2011-121689

SUMMARY OF INVENTION Technical Problem

Therefore, it is an object of the present invention to provide a belt(excluding toothed belts) which does not cause abrasion, damage, cracks,breakage, and the like on the belt body in an early stage, and is thusremarkably excellent in durability even if being used at a high load forpower transmission and the like.

Solution to Problem

As a result of exhaustive studies to achieve the above-mentioned object,the present inventors have found that if a belt body of a belt, such asa flat belt or a V-belt, is formed by using a thermoplastic resin.composition comprising a thermoplastic resin and a modified ethylenecopolymer, and obtained by dispersing the modified ethylene copolymerinto the thermoplastic resin, the belt remarkably improved in abrasionresistance and bending fatigue resistance and remarkably excellent indurability can be obtained; and this finding has led to the completionof the present invention.

That is, the present invention provides a belt (excluding toothedbelts), wherein the whole or a part of a belt body is formed from athermoplastic resin composition (C) comprising a thermoplastic resin Wand a modified ethylene copolymer (B), and obtained by dispersing themodified ethylene copolymer (B) into the thermoplastic resin (A).

The modified ethylene copolymer (B) is preferably a copolymer, modifiedwith an unsaturated carboxylic acid or a derivative thereof, of ethylenewith at least one monomer component selected from the group consistingof W olefin components except for ethylene, (ii) diene components and(iii) ester components having an ethylenically unsaturated group.

The thermoplastic resin (A) is preferably at least one selected frompolyamide resins, polyester resins, polycarbonate-based resins andpolyacetal resins.

The thermoplastic resin (A) is preferably a thermoplastic elastomer(TPE) (A1) as well. The thermoplastic elastomer (A1) is preferably atleast one selected from the group consisting of polyurethane-basedthermoplastic elastomers (A11), polyester-based thermoplastic elastomers(A12) and polyamide-based thermoplastic elastomers (A13).

The modified ethylene copolymer (B) is preferably anethylene-propylene-diene copolymerized rubber modified with anunsaturated carboxylic acid or a derivative thereof.

The weight proportion [(B)/(A)] of the modified ethylene copolymer (B)to the thermoplastic resin (A) is, for example, in the range of 0.1/99.9to 60/40.

The thermoplastic resin composition (C) preferably has a hardness (JISK6253, durometer type A) of not less than 60.

In the present description, the hardness is a value measured accordingto JIS K6253 (durometer type A). However, in Examples, there were caseswhere measurement was carried out using durometer type D (which will bedescribed to the effect).

Advantageous Effects of Invention

The belt according to the present invention, since a belt body is formedfrom a specific thermoplastic resin composition, is excellent not onlyin abrasion resistance but also in bending fatigue resistance, andhardly causes abrasion, damage, cracks, breakage and the like on thebelt body in an early stage and is remarkably excellent in durability,even if the belt is used at a high load for a long time.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a SEM photograph of a pellet. cross-section or a thermoplasticelastomer alloy (an alloy of an EPDM and an etheric TPU) obtained inComparative Example 4.

FIG. 2 is a SEM photograph of a pellet cross-section of a thermoplasticelastomer alloy (an alloy of a maleic anhydride-modified EPDM and anetheric TPU) obtained in Example 4.

FIG. 3 is a SEM photograph of a pellet cross-section of a thermoplasticelastomer alloy (an alloy of an EPDM and an esteric TPU) obtained inComparative Example 6.

FIG. 4 is a SEM photograph of a pellet cross-section of a thermoplasticelastomer alloy (an alloy of a maleic anhydride-modified EPDM and anesteric TPU) obtained in Example 7.

FIG. 5 is a graph indicating a relationship between the blend ratio of amodified ethylene copolymer in a thermoplastic resin composition and thebending fatigue resistance.

FIG. 6 is a TEM photograph of a sheet cross-section of a resincomposition obtained in Example 14.

FIG. 7 is a TEM photograph of a sheet cross-section of a resincomposition obtained in Example 19.

FIG. 8 is a TEM photograph of a sheet cross-section of a resincomposition obtained in Comparative Example 11.

FIG. 9 is an AFM photograph of a pellet. cross-section of athermoplastic elastomer alloy (an alloy of a maleic anhydride-modifiedEPDM and an etheric TPU) obtained in Example 4.

FIG. 10 is an AFM photograph of a pellet cross-section of athermoplastic elastomer alloy (an alloy of a maleic anhydride-modifiedEPDM and an esteric TPU) obtained in Example 7.

FIG. 11 is a schematic perspective diagram illustratively showing oneexample of a method for producing the belt according to the presentinvention.

DESCRIPTION OF EMBODIMENTS

The whole or a part of a belt body of the belt. according to the presentinvention is formed from a thermoplastic resin composition (C)comprising a thermoplastic resin (A) and a modified ethylene copolymer(B), and the thermoplastic resin composition (C) is obtained bydispersing the modified ethylene copolymer (B) into the thermoplasticresin (A). Here, the belt according to the present invention does notinclude toothed. belts.

In the present invention, the belt is not especially limited as long asbeing a belt excluding toothed belts, and examples thereof include knownbelts such as flat belts, V-belts and V-ribbed belts. A belt is usuallyconstituted of a belt body and core wires (tension members) embedded inthe interior of the belt body. A belt may spare core wires. A belt mayhave, as required, other members and components, coating layers and thelike. A belt may be of a single layer or may be of a two or more-layerlaminate.

Thermoplastic Resin (A)

In the present invention, as a thermoplastic resin (A), a knownthermoplastic resin can be used. The thermoplastic resin (A) can be usedsingly or in combinations of two or more. The thermoplastic resin (A)does not include a substance (compound) corresponding to a modifiedethylene copolymer (B).

Examples of the thermoplastic resin (A) include polyurethane-basedresins, polyester-based resins, polyamide-based resins, polyimide-basedresins, polystyrenic resins, polycarbonate-based resins, polyolefinicresins, acrylic resins, methacrylic resins, fluororesins, silicone-basedresins, polyacetal resins (polyoxymethylene), polyarylate resins,polyphenylene ethers, polyphenylene sulfides, polysulfones,polyethersulfones, polyetheretherketones, vinyl chloride resins andpolyvinylic resins, but are not limited thereto as long as they arecapable of dispersing a modified ethylene copolymer (B) (dispersing andcontaining a modified ethylene copolymer (B)). The thermoplastic resinmay be used singly or plurally, or may use a multicomponent singly orplurally such as copolymers, additions, blends and alloys. Thethermoplastic resin (A) has a weight-average molecular weight of, forexample, 5,000 to 1,000,000, and preferably 10,000 to 500,000.

More specific examples of the thermoplastic resin (A) include, forexample, polyamide-based resins such as polyamide 11, polyamide 12,polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 666,polyamide 46, polyamide 10T, polyamide 6T and aramid resins (wholearomatic polyamide); polyester-based resins such as polyethyleneterephthalate, polybutylene terephthalate and polyethylene naphthalate;polyimide; polystyrene; polycarbonate; polyolefinic resins such aspolyethylenes and polypropylenes; fluororesins such as polyvinylidenefluorides, polytetrafluoroethylenes, polyvinyl fluorides,polychlorotrifluoroethylenes, perflubroalkoxyfluororesins, ethylenetetrafluoride-propylene hexafluoride copolymers, ethylene-ethylenetetrafluoride copolymers and ethylene-chlorotrifluoroethylenecopolymers; polyacetal resins; polyethersulfones; polyetheretherketones;and polyvinylic resins such as polyvinyl alcohols and ethylene vinylalcohols. Additives such as reinforcing fillers such as glass fibers maybe incorporated in these thermoplastic resins (A). Also amorphousmaterials (thermoplastic resins) having no distinct melting point, inthe case of being molded by a thermoplastic resin molding machine, canbe incorporated. The thermoplastic resin (A) may be resins obtained fromfossil raw materials and natural resins as well.

Among the above, the thermoplastic resin (A) is preferably at least oneselected from the group consisting of polyamide-based resins,polyester-based resins, polycarbonate-based resins and polyacetalresins.

Thermoplastic Elastomer (A1)

As the thermoplastic resin (A), a thermoplastic elastomer (TPE) (A1) maybe preferably used. The thermoplastic elastomer (A1) comprises a hardphase (hard segment) and a soft phase (soft segment), and thoughexhibiting properties as a rubber at normal temperature, is a polymerexhibiting thermoplasticity at high temperatures. Use of thethermoplastic elastomer (A1) can improve the abrasion resistance,mechanical strength and molding processability of a thermoplastic resincomposition.

The thermoplastic elastomer (A1) may be used singly or as a mixture oftwo or more. As the thermoplastic resin (A), a thermoplastic elastomer(A1) and a resin other than a thermoplastic elastomer may beconcurrently used.

Examples of the thermoplastic elastomer (A1) include polyurethane-basedthermoplastic elastomers (A11), polyester-based thermoplastic elastomers(A12), polyamide-based thermoplastic elastomers (A13), polystyrenicthermoplastic elastomers (A14), fluoropolymer-based thermoplasticelastomers (A15), polyvinyl chloride-based thermoplastic elastomers(A16), polyolefinic thermoplastic elastomers (A17) and polyimide-basedelastomers (A18), but are not limited thereto. The thermoplasticelastomer (A1) may also be a thermoplastic elastomer in which a resin,an elastomer and/or an oligomer component are blended. (mixed). Thethermoplastic elastomer (A1) may be used singly or in combinations oftwo or more. Among the above thermoplastic elastomers (A1), preferableare polyurethane-based thermoplastic elastomer (A11), polyester-basedthermoplastic elastomers (A12) and polyamide-based thermoplasticelastomers (A13), and especially preferable are polyurethane-basedthermoplastic elastomers (A11).

Polyurethane-Based Thermoplastic Elastomer (A11)

As the polyurethane-based thermoplastic elastomer (A11), knownthermoplastic polyurethanes (TPU) can be used. The thermoplasticpolyurethane can be used singly or in combinations of two or more. Thethermoplastic polyurethane is usually obtained by reacting apolyisocyanate, a longchain polyol and a chain extender, and asrequired, other isocyanate-reactive compounds.

The polyisocyanate is not especially limited as long as it is a compoundhaving at least two isocyanate groups in the molecule. Thepolyisocyanate includes, for example, aliphatic polyisocyanates,alicyclic polyisocyanates, aromatic polyisocyanates and araliphatic(aromatic-aliphatic) polyisocyanates. The polyisocyanate can be usedsingly or in combinations of two or more.

Examples of the aliphatic polyisocyanate include aliphatic diisocyanatessuch 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate,1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate,1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylenediisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, 3-methyl-1,5-pentamethylene diisocyanate,2,4,4-trimethyl-1,6-hexamethylene diisocyanate and2,2,4-trimethyl-1,6-hexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanatessuch as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate,1,3-cyclohexane diisocyanate,3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophoronediisocyanate), 4,4′-methylenebis(cyclohexyl isocyanate),methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane and norbornane diisocyanate.

Examples of the aromatic polyisocyanate include aromatic diisocyanatessuch as m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylene diisocyanate, naphthylene 1,4-diisocyanate,naphthylene 1,5-diisocyanate, 4,4′-diphenyl diisocyanate (4,4′-biphenyldiisocyanate), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethanediisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenyl etherdiisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate,3,3′-dimethyldiphenylmethane-4,4′-diisocyanate and 4,4′-diphenylpropanediisocyanate.

Examples of the araliphatic polyisocyanate include araliphaticdiisocyanates such as 1,3-xylylene diisocyanate, 1,4-xylylenediisocyanate, ω,ω′-diisocyanato-1,4-diethylbenzene,1,3-bis(1-isocyanato-1-methylethyl)benzene,1,4-bis(1-isocyanato-1-methylethyl) benzene and1,3-bis(α,α-dimethylisocyanatomethyl)benzene.

As the polyisocyanate, suitably usable are 1,6-hexamethylenediisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate),1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,4,4′-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate,1,4-xylylene diisocyanate, norbornane diisocyanate and1,3-bis(α,α-dimethylisocyanatomethyl)benzene.

As the polysocyanate, also usable are dimers, trimers, reaction productsor polymers of the above exemplified aliphatic polyisocyanates,alicyclic polyisocyanates, aromatic polysocyanates and araliphaticpolyisocyanates (for example, a dimmer or a trimer of diphenylmethanediisocyanate, reaction products of trimethylolpropane and tolylenediisocyanate, reaction products of trimethylolpropane and hexamethylenediisocyanate, polymethylene polyphenyl isocyanates, polyetherpolyisocyanates, polyester polyisocyanates and the like) and the like.

Examples of the long-chain polyol include polyether polyols, polyesterpolyols, polycarbonate polyols, polyolefin polyols and polyacrylpolyols. The long-chain polyol has a number-average molecular weight ofusually not less than 500, preferably 500 to 10,000, still morepreferably 600 to 6,000, and further still more preferably 800 to 4,000.The long-chain polyol can be used singly or in combinations of two ormore.

Examples of the polyether polyol include polyalkylene ether glycols suchas polyethylene ether glycols, polypropylene ether glycols andpolytetramethyiene ether glycols (PTMG), and additionally copolymerscontaining a plurality of alkylene oxides (alkylene oxide-anotheralkylene oxide) as monomer components, such as ethylene oxide-propyleneoxide copolymers. Among the polyether polyols, especially preferable arepolytetramethylene ether glycols (PTMG).

As the polyester polyol, usable are, for example, polycondensates of apolyhydric alcohol and a polyvalent. carboxylic acid, ring-openedpolymers of cyclic esters (lactones), and reaction products of threecomponents of a polyhydric alcohol, a polyvalent carboxylic acid and acyclic ester (lactone). In the polycondensates of a polyhydric alcoholand a polyvalent carboxylic acid, as the polyhydric alcohol, usable are,for example, ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol,2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol,1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol,1,9-nonanediol, 1,10-decanediol, glycerol, trimethylolpropane,trimethylolethane, cyclohexanediols (1,4-cyclohexanediol and the like),cyclohexanedimethanols (1,4-cyclohexanedimethanol and the like),bisphenols (bisphenol A and the like), and sugar alcohols (xylitol,sorbitol and the like). On the other hand, examples of the polyvalentcarboxylic acid include aliphatic dicarboxylic acids such as malonicacid, maleic acid, succinic acid, glutaric acid, adipic acid, subericacid, azelaic acid, sebacic acid and dodecanedioic acid; alicyclicdicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; andaromatic dicarboxylic acids such as terephthalic acid, isophthalic acid,orthophthalic acid, 2,6-naphthalenedicarboxylic acid,para-phenylenedicacboxylic acid and trimellitic acid. In the ring-openedpolymers of cyclic esters, examples of the cyclic ester includepropiolactone, β-methyl-δ-valerolactone and α-caprolactone. In thereaction products of three components, the above exemplified polyhydricalcohols, polyvalent carboxylic acids and cyclic esters and the like canbe used. Among the polyester polyols, preferable are adipate-basedpolyester polyols [for example, C2-6 alkylene adipates such as poly(ethylene adipate), poly(diethylene adipate), poly(propylene adipate),poly(tetramethylene adipate), poly(hexamethylene adipate) andpoly(neopentylene adipate)] which are polycondensates of adipic acid anda polyhydric alcohol (for example, one or two or more of alkane diolshaving 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol,neopentyl glycol and 1,6-hexanediol), caprolactone polyols obtained byring-opening polymerization of ε-caprolactone, polyester polyolsobtained by ring-opening polymerization of β-methyl-8-valerolactoneusing a polyhydric alcohol such as ethylene glycol, and the like.

Examples of the polycarbonate polyol include reaction products of apolyhydric alcohol and phosgene, a chloroformate ester, a dialkylcarbonate or a diaryl carbonate (a polyhydric alcohol and a compoundselected from the group consisting of phosgene, a chloroformate ester, adialkyl carbonate and a diaryl carbonate); and ring-opened polymers ofcyclic carbonate esters (alkylene carbonates and the like). In thereaction products of a polyhydric alcohol and phosgene, as thepolyhydric alcohol, specifically usable are the above exemplifiedpolyhydric alcohols (for example, ethylene glycol, propylene1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol,1,6-hexanediol and 1,9-nonanediol). In the ring-opened polymers ofcyclic carbonate esters, examples of the alkylene carbonate includeethylene carbonate, trimethylene carbonate, tetramethylene carbonate andhexamethylene carbonate. Here, the polycarbonate polyol suffices ifbeing a compound having carbonate bonds in the molecule and havinghydroxyl groups at the terminals, and may have ester bonds together withthe carbonate bonds. Typical examples of the polycarbonate polyolinclude poly(hexamethylene carbonate) diols, diols obtained byring-opening addition polymerization of a lactone to apoly(hexamethylene carbonate) diol, and cocondensates of apoly(hexamethylene carbonate) dial and a polyester diol or a polyetherdiol.

The polyolefin polyol is a polyol having an olefin as a component of askeleton (or a main chain) of a polymer or a copolymer, and having atleast two hydroxyl groups in the molecule (particularly at theterminals). The above olefin may be an olefin (for example, an α-olefinsuch as ethylene or propylene) having a carbon-carbon double bond at theterminal, may be an olefin (for example, isobutene) having acarbon-carbon double bond at a site other than the terminals, or furthermay be a diene (for example, butadiene or isoprene). Typical examples ofthe polyolefin polyol include substances (compounds) obtained bymodifying, with hydroxyl groups, the terminals of butadiene- orisoprene-based polymers such as butadiene homopolymers, isoprenehomopolymers, butadiene-styrene copolymers, butadiene-isoprenecopolymers, butadiene-acrylonitrile copolymers, butadiene-2-ethylhexylacrylate copolymers, butadiene-n-octadecyl acrylate copolymers.

The polyacryl polyol is a polyol having a (meth)acrylate as a componentof a skeleton (or a main chain) of a polymer or a copolymer, and havingat least two hydroxyl groups in the molecule (particularly at theterminals). As the (meth)acrylate, suitably used are alkyl(meth)acrylate esters [for example, C₁₋₂₀ alkyl (meth)acrylate esters].As the polyol, every material other than materials cited here can beused.

As the chain extender, usable are chain extenders usually used inproduction of thermoplastic polyurethanes, and the type thereof is notespecially limited, and low-molecular weight polyols and polyamines andthe like can be used. The chain extender has a molecular weight ofusually less than 500, and preferably not more than 300. The chainextender can be used singly or in combinations of two or more.

Typical examples of the chain extender include polyols (particularly,dials) such as ethylene glycol, diethylene glycol, propylene glycol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,1,2-pentanediol, 2,3-pentanediol, neopentyl glycol, 1,6-hexanediol,3-methyl-1,5-pentanediol, 1,4-cyclohexanediol and1,4-cyclohexanedimethanol, and polyamines (particularly, diamines) suchas hexamethylenediamine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethaneand 4,4′-methylenebis-2-chloroaniline. Among these, dials are especiallypreferable.

As the thermoplastic polyurethane, preferable are thermoplasticpolyurethanes obtained by reacting polyisocyanate, a long-chain polyoland a chain extender in the range of the ratio (NCO/isocyanate-reactivegroups), of the molar number of isocyanate groups of the polyisocyanateand the molar number of isocyanate-reactive groups (hydroxyl group,amino group and the like) of the long-chain polyol and the chainextender, of 0.9 to 1.3, especially 0.95 to 1.1. The proportion of thelong-chain polyol to the chain extender, [the former/the latter (molarratio)], can suitably be selected in the range of, for example, 0.1 to1.0, and preferably 0.2 to 2, according to physical properties and thelike of the thermoplastic polyurethane. In the above reaction, in orderto promote the reaction, as required, a catalyst such as a tertiaryamine, an organometal compound or a tin compound may be used.

The thermoplastic polyurethane usually has a weight-average molecularweight Mw of 5,000 to 1,000,000. The thermoplastic polyurethane hasthermoplasticity, though some exhibit no distinct melting point. Thethermoplastic polyurethane has thermoplasticity, and can be molded by acommon thermoplastic resin molding machine such as extrusion, injectionmolding, heat press or the like.

The hardness of the thermoplastic polyurethane, but not limited to, fromthe viewpoint of raising mechanical properties of the thermoplasticresin composition (thermoplastic elastomer alloy and the like) accordingto the present invention, is preferably not less than 60 (for example,60 to 96), more preferably not less than 78 (for example, 78 to 96),still more preferably not less than 89 (for example, 89 to 95), andespecially preferably not less than 91 (for example, 91 to 94), inhardness of JIS K6253 (durometer type A). From the viewpoint of lettingthe thermoplastic resin composition (thermoplastic elastomer alloy andthe like) have reasonable flexibility and raising the bending fatigueresistance, the thermoplastic polyurethane has a hardness in the rangeof, for example, 60 to 93, and especially preferably 78 to 91(particularly 78 to 88).

The thermoplastic polyurethane preferably uses a polyester polyol or apolyether polyol as the long-chain polyol. Among these, thethermoplastic polyurethane is especially preferably adipate-based TPUsusing an adipate-based polyester polyol as the long-chain polyol,caprolactone-based TPUs using a caprolactone polyol as the long-chainpolyol, and PTMG-based TPUs using a polytetramethylene ether glycol(PTMG) as the long-chain polyol.

As the thermoplastic polyurethane, commercially available products canbe used. Examples of the commercially available products include anadipate-based TPU of 80 in hardness (an adipate-based TPU with ahardness of 80, a hardness of 80), an adipate-based TPU of 90 inhardness, a caprolactone-based TPU of 90 in hardness, a PTMG-based TPUof 92 in hardness, and an adipate-based TPU of 92 in hardness.

Polyester-Based Thermoplastic Elastomer (A12)

As the polyester-based thermoplastic elastomer (A12), knownpolyester-based thermoplastic elastomers can be used. Thepolyester-based thermoplastic elastomer (A12) can be used singly or incombinations of two or more.

The polyester-based thermoplastic elastomer (A12) can be produced by aknown method such as the esterification reaction or thetransesterification reaction.

The polyester-based thermoplastic elastomer (A12) is preferably, forexample, polyester-based thermoplastic elastomers having as mainconstituting units a hard segment composed of an aromatic polyester unitand a soft segment composed of an aliphatic polyether unit and/or analiphatic polyester unit.

The aromatic polyester unit is mainly a unit formed of an aromaticdicarboxylic acid or an ester-forming derivative thereof (a C₁₋₄ alkylester, an acid halide or the like) and a diol or an ester-formingderivative thereof (an acetylated derivative, an alkaline metal salt orthe like). Specific examples of the aromatic dicarboxylic acid includeterephthalic acid, isophthalic acid, phthalic acid,naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid,anthracenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid,diphenoxyethanedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid,5-sulfoisophthalic acid and sodium 3-sulfoisophthalate. Specificexamples of the diol include dials having a molecular weight of not morethan 400, and include, for example, aliphatic diols such as1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethyleneglycol, hexamethylene glycol and neopentyl glycol, decamethylene glycol;alicyclic diols such as 1,1-cyclohexanedimethanol,1,4-dicyclohexanedimethanol and tricyclodecanedimethanol; and aromaticdiols such as xylylene bis(p-hydroxy)diphenyl,bis(p-hydroxy)diphenylpropane,2,2′-bis[(4-(2-hydroxyethoxy)phenyl)]propane,bis[4-(2-hydroxyethoxy)phenyl]sulfone,1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane and4,4′-dihydroxy-p-terphenyl. These aromatic dicarboxylic acids orester-forming derivatives thereof, and diols and ester-formingderivatives thereof may be concurrently used in two or more,respectively. Preferable aromatic polyester units include a polybutyleneterephthalate unit derived from terephthalic acid and/or dimethylterephthalate and 1,4-butanediol, and a unit composed of a polybutyleneterephthalate unit derived from terephthalic acid and/or dimethylterephthalate and a polybutylene isophthalate unit derived fromisophthalic acid and/or dimethyl isophthalate and 1,4-butanediol.

Examples of an aliphatic polyether constituting the aliphatic polyetherunit include poly (ethylene oxide) glycols, poly (propylene oxide)glycols, poly(tetramethylene oxide) glycols, poly(hexamethylene oxide)glycols, copolymers of ethylene oxide and propylene oxide, ethyleneoxide addition polymers of poly(propylene oxide) glycols and copolymerglycols of ethylene oxide and tetrahydrofuran. Among these, preferableare poly(tetramethylene oxide) glycols, ethylene oxide addition productsof poly (propylene oxide) glycols and copolymer glycols of ethyleneoxide and tetrahydrofuran. Examples of an aliphatic polyesterconstituting the aliphatic polyester unit include poly(ε-caprolactone)s,polyenantholactones, polycaprolactones, polybutylene adipates andpolyethylene adipates. Among these, preferable arepoly(ε-caprolactone)s, polybutylene adipates, polyethylene adipates, andthe like.

The soft segment composed of an aliphatic polyether unit and/or analiphatic polyester unit has a number-average molecular weight ofpreferably 300 to 6,000, and especially preferably 500 to 4,000, in thecopolymerized state.

The ratio of the hard segment composed of an aromatic polyester unit andthe soft segment composed of an aliphatic polyether unit and/or analiphatic polyester unit in the polyester-based thermoplastic elastomeris not especially limited, but is, for example, the former/the latter(weight ratio)=1/99 to 99.5/0.5, and preferably 50/50 to 99/1.

Polyamide-Based Thermoplastic Elastomer (A13)

As the polyamide-based thermoplastic elastomer (A13), knownpolyamide-based thermoplastic elastomers can be used. Thepolyamide-based thermoplastic elastomer (A13) can be used singly or incombinations of two or more.

As the polyamide-based thermoplastic elastomer (A13), preferable are,for example, polyamide-based the elastomers having as main constitutingunits a hard segment composed of a polyamide unit and a soft segmentcomposed of an aliphatic polyether unit and/or an aliphatic polyesterunit.

Examples of a polyamide constituting the polyamide unit include nylon 6,nylon 66, nylon 11 and nylon 12. Examples of an aliphatic polyetherconstituting the aliphatic polyether unit include the same aliphaticpolyethers as exemplifed in the term of the polyester-basedthermoplastic elastomer. Among these, preferable are poly(tetramethyleneoxide) glycols, ethylene oxide additions of poly (propylene oxide)glycols, and copolymer glycols of ethylene oxide and tetrahydrofuran.Examples of an aliphatic polyester constituting the aliphatic polyesterunit include the same aliphatic polyesters as exemplified in the term ofthe polyester-based thermoplastic elastomer. Among these, preferable arepoly(ε-caprolactone)s, polybutylene adipates, polyethylene adipates, andthe like.

Other Thermoplastic Elastomers

As the polystyrenic thermoplastic elastomer (A14), thefluoropolymer-based thermoplastic elastomer (A15), the polyvinylchloride-based thermoplastic elastomer (A16), the polyolefinicthermoplastic elastomer (A17) and the polyimide-based elastomer (A18),usable are respective known elastomers.

As the thermoplastic resin (A), from the viewpoint of the adhesion witha modified ethylene copolymer (B), preferable are resins having, in themolecule (for example, on the main chain, terminals and side chains of apolymer), functional groups (or functional groups having affinity)reactive, in heating and mixing, with modifying groups (for example, acarboxyl group or its salt, a carboxylate ester group, an acid anhydridegroup, a carboxylic acid halide group, an amido group, an imido group, aglycidyl group (epoxy group), a halogen atom, an amino group, an imidogroup, a phosphino group, a thioxy group and a silicon-containing group,which will be described later) of the modified ethylene copolymer (B).Examples of such a resin include thermoplastic resins having, on theterminals of a polymer main chain, functional groups such as a hydroxylgroup, a carboxyl group, an amino group and a thiol group, for example,polyamide-based resins, polyester-based resins, polycarbonate-basedresins, polyacetal resins, polyphenylene ethers, polyphenylene sulfides,polyurethane-based thermoplastic elastomers (A11), polyester-basedthermoplastic elastomers (A12) and polyamide-based thermoplasticelastomers (A13).

Modified Ethylene Copolymer (B)

In the present invention, as the modified ethylene copolymer (B), usableare known modified ethylene copolymers. The modified ethylene copolymer(B) can be used singly or in combinations of two or more. The modifiedethylene copolymer (B) has a weight-average molecular weight of, forexample, 5,000 to 1,000,000, and preferably 10,000 to 500,000.

The modified ethylene copolymer (B) is an ethylene copolymer modifiedwith an unsaturated carboxylic acid or a derivative thereof or anotherfunctional group. Examples of the ethylene copolymer include copolymersof ethylene with at least one monomer component selected from (i) olefincomponents except ethylene, (ii) diene components and (iii) estercomponents having an ethylenically unsaturated group. Examples of theolefin component except for ethylene include α-olefins having 3 to 12carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene and 1-decene. Examples of the diene componentinclude non-conjugated dienes such as ethylidene norbornene,dicyblopentadiene and 1,4-hexadiene. Examples of the ester componenthaving an ethylenically unsaturated group include alkyl (meth)acrylateesters such as methyl (meth) acrylate and ethyl (meth)acrylate, andvinyl carboxylate esters such as vinyl acetate and vinyl propionate.

Typical examples of the ethylene copolymer includeethylene-propylene-diene copolymers (ethylene-propylene-dienecopolymerized rubber, ethylene-propylene-diene rubbers; EPDM),ethylene-propylene copolymers (ethylene-propylene rubbers; EPM),ethylene-methyl (meth acrylate copolymers, ethylene-ethyl (meth)acrylatecopolymers and ethylene-vinyl acetate copolymers. Among these,especially preferable are ethylene-propylene-diene copolymers(ethylene-propylene-diene rubbers; EPDM) and ethylene-propylenecopolymers (ethylene-propylene rubbers; EPM).

Examples of an unsaturated carboxylic acid used for modification of theethylene copolymer include acrylic acid, methacrylic acid, maleic acid,fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,crotonic acid, isocrotonic acid and norbornenedicarboxylic acid.Examples of a derivative of an unsaturated carboxylic acid includeesters of unsaturated carboxylic acids [for example, glycidyl(meth)acrylate and maleate esters], acid anhydrides (maleic anhydrideand the like), salts, acid halides, amides and imides. An ethylenecopolymer modified with an unsaturated carboxylic acid or a derivativethereof has, in the molecule, a carboxyl group or a salt thereof, acarboxylate ester, an acid anhydride group, a carboxyl acid halidegroup, an amido group, an imido group or the like.

Other functional groups used for modification of the ethylene copolymerare not especially limited as long as they are capable of chemicallymodifying the ethylene copolymer. The other functional groups include,for example, a glycidyl group (epoxy group), a halogen atom, an aminogroup, an imido group, a phosphino group, a thioxy group, a siliconatom-containing group. These functional groups may be incorporatedsingly or in two or more.

Modification of an ethylene copolymer can be carried out, for example,by heating and kneading the ethylene copolymer and an unsaturatedcarboxylic acid or a derivative thereof in the presence of a graftpolymerization. initiator [for example, a peroxide initiator such as1,3-bis(t-butylperoxyisopropyl)benzene or dicumyl peroxide].Modification of an ethylene copolymer can be carried out also by furtherusing an unsaturated carboxylic acid (acrylic acid, methacrylic acid orthe like) as another comonomer when ethylene and a comonomer such as anester having an ethylenically unsaturated bond [methyl (meth)acrylate,ethyl (meth) acrylate, vinyl acetate or the like] are copolymerized.Further, modification of an ethylene copolymer with the above anotherfunctional group can also be carried out by a known method. Modificationmay use a chemical reaction such as random copolymerization, alternatingcopolymerization, block copolymerization or graft copolymerization, mayuse a state of a reaction intermediate, or may use a physicalmodification such as addition, coexistence or generation.

The modification ratio with an unsaturated carboxylic acid or aderivative thereof or the another functional group in the modifiedethylene copolymer (B) is, as a content rate of a structural unitcontaining groups originated (derived) from the unsaturated carboxylicacid or the derivative thereof, or a structural unit containing theanother functional group, for example, about 0.1 to 20 wt %, preferablyabout 0.5 to 10 wt %, and still more preferably about 1 to 8 wt %, withrespect to the whole modified ethylene copolymer (a whole amount of themodified ethylene copolymer). If the content rate is too low, theimproving effect of the abrasion resistance and the bending fatigueresistance in blending with a thermoplastic resin (A) is liable tobecome small. By contrast, if the content rate is too high, propertiesas a copolymer intrinsic to an ethylene copolymer become liable todecrease, making difficult the maintenance of the copolymer and alsomaking difficult the regulation of the properties.

The modification of an ethylene copolymer may be carried outindependently for the ethylene copolymer before being blended with athermoplastic resin, or may be carried out simultaneously in a stage ofblending a before-modification ethylene copolymer with a thermoplasticresin. An unreacted carboxylic acid or derivative thereof may beremoved, or may be used as it remains.

The modified ethylene copolymer (B) is preferably a copolymer, modifiedwith an unsaturated carboxylic acid or a derivative thereof, of ethylenewith at least one monomer component selected from (i) olefin componentsexcept for ethylene (particularly, α-olefins containing at leastpropylene), (ii) diene components and (iii) ester components having anethylenically unsaturated group. Among these, especially preferable arepolymers obtained by modifying a copolymer of ethylene, an olefin exceptfor ethylene (particularly, α-olefin containing at least propylene)and/or a diene with an unsaturated carboxylic acid or a derivativethereof (particularly maleic anhydride).

A preferable modified ethylene copolymer (B) includes modifiedethylene-propylene-diene copolymerized rubbers (modified EPDM) (B1),modified ethylene-propylene rubbers (modified EPM) (B2) and carboxylicacid-modified ethylene acryl rubbers (acid-modified ethylene acrylelastomers) (B3). Among these, preferable are modifiedethylene-propylene-diene copolymerized rubbers (modified EPDM) (B1).

Modified Ethylene-Propylene-Diene Copolymerized Rubber (B1)

In the present invention, as the modified ethylene-propylene-dienecopolymerized rubber (B1) (modified EPDM), usable are known modifiedethylene-propylene-diene copolymerized rubbers. The modifiedethylene-propylene-diene copolymerized rubber (B1) can be used singly orin combinations of two or more.

An ethylene-propylene-diene copolymer (EPDM) is a copolymer or ethylene,propylene and a non-conjugated diene. Examples of the diene include5-ethylidene-2-norbornene, dicyclopentadiene and 1,4-hexadiene. Amodified ethylene-propylene-diene copolymerized rubber (modified EPDM)(B1) used in the present invention is obtained by modifying an EPDMwith, for example, an unsaturated carboxylic acid or a derivativethereof (an ester, an acid anhydride, a salt, an acid halide, an amide,an imide, or the like) or another functional group. Examples of theunsaturated carboxylic acid or the derivative thereof include, as in theabove, acrylic acid, methacrylic acid, maleic acid, fumaric acid,tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,isocrotonic acid, norbornenedicarboxylic acid, glycidyl (meth)acrylate,maleate esters and maleic anhydride, and the unsaturated carboxylic acidor the derivative thereof may have a structure of an ester salt, a metalsalt thereof and the like. Among these, preferable are acrylic acid,methacrylic acid and maleic anhydride, and especially preferable ismaleic anhydride. The another functional group includes, for example, aglycidyl group, a halogen atom, an amino group, an imido group, aphosphino group and a thioxy group.

Modification of an EPDM can be carried out, for example, by heating andkneading the EPDM and an unsaturated carboxylic acid or a derivativethereof in the presence of a graft polymerization initiator [forexample, a peroxide initiator such. as1,3-bis(t-butylperoxyisopropyl)benzene or dicumyl peroxide]. The ratioof ethylene and propylene in an EPDM used as a raw material is, from theviewpoint of properties thereof as an elastomer, and the like, forexample, the former/the latter (weight ratio) =10/90 to 95/5, andpreferably about 50/50 to 85/15. The content rate of a structural unitoriginated from a diene component in an EPDM is, for example, about 0.1to 25 wt %, preferably about 1 to 20 wt %, and more preferably about 2to 10 wt %, to the whole EPDM.

The modification ratio with an unsaturated carboxylic acid or aderivative thereof in the modified ethylene-propylene-dienecopolymerized rubber (B1) is, as a content rate of a structural unitoriginated from the unsaturated carboxylic acid or the derivativethereof, for example, about 0.1 to 20 wt. %, preferably about 0.5 to wt%, and more preferably about. 1 to 8 wt %, with respect to the wholemodified EPDM. If the content rate is too low, the improving effect ofthe abrasion resistance and the bending fatigue resistance in blendingwith a thermoplastic resin (A) [for example, the polyurethane-basedthermoplastic elastomer (A1)] is liable to become small. By contrast, ifthe content rate is too high, the function as an elastomer becomesliable to decrease.

The modification of an EPDM may be carried out independently for theEPDM before being blended with a TPU, or may be carried outsimultaneously in a stage of blending a before-modification EPDM with aTPU. An unreacted carboxylic acid or a derivative thereof may beremoved, or may be used as it remains.

The modified ethylene-propylene-diene copolymerized rubber (B1) has amelt flow rate (ASTM D1238, 280° C./2.16 kg) of, for example, 5 to 80g/10-min, and. preferably 10 to 40 g/10-min.

As the modified ethylene-propylene-diene copolymerized rubber (B1),commercially available products may be used. Examples of thecommercially available product include “Fusabond N416” by trade name(maleic anhydride-modified EPDM, Du Pont K. K.)

A modified ethylene-propylene-diene copolymerized rubber (B1) to becomea dispersoid in a resin composition may be crosslinked, uncrosslinked.For example, dynamic crosslinking means, in which crosslinking iscarried out with thermoplasticity being maintained, may be used.

Although a modified ethylene-propylene-diene copolymerized rubber (B1)is often crosslinked and then utilized as industrial rubber products sofar, and has not been so much used as a modifier for other resins, ithas been found according to the present invention that making thecopolymerized rubber dispersed and contained in a thermoplastic resincan remarkably improve properties of the thermoplastic resin.

As the modified ethylene-propylene copolymerized rubber (modified ETM)(B2) as well, known n modified ethylene-propylene copolymerized rubberscan be used. The modified ethylene-propylene copolymerized rubber can beused singly or in combinations of two or more. An ethylene-propylenecopolymer (EPM) is a copolymer of ethylene and propylene, and themodification of the EPM can be carried out similarly to the modificationof the EPDM. As the acid-modified ethylene acryl elastomer (B3) as well,known acid-modified ethylene acryl elastomers can be used. Theacid-modified ethylene acryl elastomer (B3) can be used singly or incombinations of two or more.

Thermoplastic Resin Composition (C)

The thermoplastic resin composition (C) according to the presentinvention is a resin composition comprising the thermoplastic resin (A)and the modified ethylene copolymer (B), and the thermoplastic resincomposition (C) is obtained by dispersing the modified ethylenecopolymer (B) into the thermoplastic resin (A) ((a resin compositioncomprising the thermoplastic resin W and the modified ethylene copolymer(B), and obtained by dispersing the modified ethylene copolymer (B) intothe thermoplastic resin (A)), as described above.

In the present invention, the weight proportion [(B)/(A)] of the (B) to(A) is, though depending on the kinds of the components (A) and (B),usually in the range of 0.1/99.9 to 60/40. The lower limit of theproportion (ratio) is preferably 1/99, more preferably 3/97, andespecially preferably 7.5/92.5; and the upper limit thereof ispreferably 55/45, more preferably 50/50, still more preferably 30/70,and especially preferably 25/75 (particularly, 22/78). Morespecifically, the weight proportion [(B)/(A)] of the (B) to (A) ispreferably 0.1/99.9 to 30/70, more preferably 1/99 to 25/75, and stillmore preferably 3/97 to 22/78 (particularly, 7.5/92.5 to 22/78). If theproportion is too low, the improving effect of the durability of theabrasion. resistance, and the bending fatigue resistance becomes small.By contrast, if the proportion is too high, properties (mechanicalstrength and the like) intrinsic to the thermoplastic resin becomeliable to decrease.

The present inventors have found that in a resin composition which isobtained by dispersing a modified ethylene copolymer into athermoplastic resin and which comprises the thermoplastic resin and themodified ethylene copolymer, the durability such as the bending fatigueresistance of molded articles of the resin composition exhibits a moreimproved value than a value anticipated for the each material as asingle material. That is, it has been found that an actually acquiredvalue of the bending fatigue resistance of a blend of a thermoplasticresin W and a modified ethylene copolymer (B) is higher than a valuethereof calculated on the assumption of the additivity being held in theblend, thus providing a synergistic effect. For example, in FIG. 5[which is a graph indicating a relationship between the blend ratio (wt%) of a modified ethylene copolymer (MAE-EPDM) and the bending fatigueresistance, based on data of Examples and Comparative Examples describedlater], a line (dotted line in FIG. 5) connecting values of the bendingnumbers of times by a straight line in the cases of the blend ratio ofMAH-EPDM being 0 wt % and 100 wt % indicates values of the bendingnumbers of times in respective blend ratios on the assumption of theadddtivity being held. By contrast, the result of a resin composition(solid line in FIG. 5) is a result of the bending numbers of times,which are by far more than the dotted line, thus being conceivably asynergistic effect. The synergistic effect is large in the case of usinga thermoplastic elastomer (A1) as the thermoplastic resin (A) (forexample, a polyurethane-based thermoplastic elastomer), and isremarkable particularly in the case of using a modifiedethylene-propylene-diene copolymerized rubber as the modified ethylenecopolymer (B).

In the thermoplastic resin composition (C), in addition to the above and(B), as required, additives can be blended. Examples of the additivesinclude antioxidants, ultraviolet absorbers, plasticizers, stabilizers,mold lubricants, surfactants, antistatic agents, electroconductivematerials, colorants (pigments, dyes), flame retardants, foaming agents,slip agents, lubricants, bulking agents, crosslinking agents, solvents,developing solutions, extenders, waxes, oils, greases, processing aids,processing agents, reinforcing materials, fillers, antiblocking agentsand antiaging agents.

In the thermoplastic resin composition (C), in addition to the above (A)and (B), as required, reinforcing materials can be incorporated.Examples of the reinforcing materials include fibers, powders, clothes,substrate materials, long fibers, short fibers, glass clothes, fabrics,carbon nanotubes, fullerenes, graphites, carbon blacks, silicas, foams,beads, inorganic fillers, heat dissipation fillers, electroconductivefillers, ceramics, fine ceramics and carbon fibers.

In the thermoplastic resin composition (C), the total content of thethermoplastic resin (A) and the modified ethylene copolymer (B) is, forexample, not less than 60 wt %, preferably not less than 80 wt %, andmore preferably not less than 90 wt %.

The modified ethylene copolymer (B) in the thermoplastic resincomposition (C) has preferably an average dispersed particle aspectratio (=major diameter/minor diameter) of 1 to 3.5, more preferably 1 to3, and much more preferably 1 to 2. An average dispersed particle aspectratio near 1 means that in an actual the resin composition, the shape(disperse shape) of the (B) dispersed is near a true sphere. Here, theaverage dispersed particle aspect ratio is calculated from a majordiameter/a minor diameter of island phases (disperse phase) in aplanarized visual field when a disperse state of a material at anarbitrary place of a thermoplastic resin composition is observed byknown means (SEM, TEM, AFM or the like). The modified ethylene copolymer(B) in the thermoplastic resin composition (C) has preferably an averagedispersed particle diameter of not more than 3 μm, and more preferablynot more than 1 μm. An average dispersed particle aspect ratio nearer 1,that is, nearer a true sphere, is better. A smaller average dispersedparticle diameter is better. If the average dispersed particle aspectratio is in the above range, since the degree of anisotropicity is verylow and there is no directivity, a high rigidity is exhibited onstresses from every direction. Consequently, the dispersed particleexhibits the effect as a reinforcing filler in every direction.

The average dispersed particle aspect ratio and the average dispersedparticle diameter can be measured by a scanning electron microscope(SEM), a transmission electron. microscope (TEM), further an atomicforce microscope (AFM), and the like.

The hardness of the thermoplastic resin composition (C) is notespecially limited, but the hardness in JIS K6253 (durometer type A) ispreferably not less than 60 (for example, 60 to 95), more preferably notless than 78 (for example, 78 to 95), still more preferably not lessthan 89 (for example, 89 to 95), and especially preferably not less than91 (for example, 91 to 95). From the viewpoint of having a reasonableflexibility and enhancing the bending fatigue resistance, the hardnessof the thermoplastic resin composition (C) is, for example, in the rangeof^(.) 60 to 93, and especially preferably in the range of 77 to 91(particularly 77 to 88). The hardness of the thermoplastic resincomposition (C) can be regulated by the hardness of a thermoplasticresin (A), the weight proportion of the modified ethylene copolymer (B)to the thermoplastic resin (A), the kinds and amounts of additives, andthe like.

The breaking strength (JIS K7311) of the thermoplastic resin composition(C) depends largely on a resin to become a continuous phase (sea phase).The breaking strength (JIS K7311) of the thermoplastic resin.composition (C) is, for example, 25 to 100 MPa, preferably 30 to 80 MPa,and more preferably 35 to 75 MPa; and the breaking elongation (JISK7311) is, for example, 300 to 1,000%, preferably 350 to 800%, and morepreferably 400 to 700%.

The thermoplastic resin. composition. (C) can be produced by mixing thethermoplastic resin (A), the modified ethylene copolymer (B), and theadditives used according to needs by the same method as the case ofpreparing usual polymer alloys or polymer blends. For example, thethermoplastic resin composition can be produced by pre-mixing thethermoplastic resin (A), the modified ethylene copolymer (B), and theadditives used according to needs in predetermined proportions, andthereafter, kneading the mixture under heating, under pressure, in thepresence of a solvent or the like by using a single-screw extruder, atwin-screw extruder, a mixing roll, a Banbury mixer, a batch-typekneader, a reactor, a reactive molding machine, an injection moldingmachine or the like. In the case of carrying out heating and kneadingusing an extruder, the composition extruded in a strand form, and may becut into a suitable length to thereby make a granule such as a pellet.Besides the above method, the thermoplastic resin composition (C) can beproduced also by charging and mixing the modified ethylene copolymer (B)and/or the additives during the production of the thermoplastic resin(A). In the case of using a thermoplastic elastomer (A1) such as athermoplastic polyurethane (polyurethane-based thermoplastic elastomer)as the thermoplastic resin (A), a thermoplastic elastomer alloy can beobtained.

The average dispersed particle aspect ratio and the average dispersedparticle diameter of the modified ethylene copolymer (B) in thethermoplastic resin composition (C) can be regulated by the kinds andthe degrees of crosslinking of the thermoplastic resin (A) and themodified ethylene copolymer (B), the viscosity ratio and the volumeratio of the thermoplastic resin (A) and the modified ethylene copolymer(B), the magnitude of a shearing force impressed in kneading a mixturecontaining the thermoplastic resin (A) and the modified ethylenecopolymer (B), and the like. In more detail, the disperse state of thecomposition can be controlled by regulating respective amounts (vol %)and shearing viscosities of the thermoplastic resin (A) and the modifiedethylene copolymer (B) and regulating a molding method and the like, forexample, at a temperature and a shearing rate at which both thethermoplastic resin (A) and the modified ethylene copolymer (B) becomeflowable. In a completely incompatible blend system, the case where onecomponent has a higher vol % than the other or the case where onecomponent has a lower shearing viscosity than the other basically takesa sea-island structure; and the higher-vol % and/or lower-shearingviscosity component forms a sea side (continuous phase). The case whererespective vol % and shearing viscosities approach closely provides astructure in which both components form micro-continuous phases. On theother hand, the case where the shearing viscosity of a sea componentbecomes higher than that of an island component due to a reaction of thecomponents during kneading includes a case where the sea-islandstructure reverses during the kneading; and a dual-continuous phasedevelops, though being a very complicate structure, during the phasetransformation. The reaction used here may be a crosslinking (curing) ofone component, or may involve a viscosity decrease due to a molecularweight decreasing phenomenon by transesterification, hydrolysis and thelike of the other component. In the case of a dual-continuous phase,although the average dispersed particle aspect ratio becomes large,since a shearing force can be most highly transmitted to bothcomponents, a micro-dispersion can be provided if kneading is carriedout through this process. Further in a. sea-island structure, withrespect to the shape of the island side, a shape near a spherical one isresultantly obtained in the case where an island-side resin is stronglyand quickly kneaded in a sea-side resin having a relatively low shearingviscosity as compared with the island side rather than in the case whereboth the components have shearing viscosities close to each other. Forexample, by using the above-mentioned resin kneading machine for asuitable time (for example, 30 sec to 15 min) and at a suitable shearingforce according to the materials and the like, the average dispersedparticle aspect ratio and the average dispersed particle diameter of themodified ethylene copolymer (B) can be made in the above-mentionedrange. The composition is returned to normal temperature at a rate asnear quenching as possible so that these disperse states are notdestroyed. Thereby, a thermoplastic resin composition having a desiredfixed disperse state can be obtained. As described above, thesimultaneous satisfaction of both the spherical dispersion and themicro-dispersion is difficult.

However, by designing the viscosities, the amounts and the kinds ofcomponents of the thermoplastic resin composition, the kneading methodand the molding condition, the present invention can achieve thesimultaneous satisfaction of both, and can obtain a thermoplastic resincomposition more excellent in the durability.

The thermoplastic resin composition (C) can be subjected to meltmolding, thermal processing, press molding and the like, and can providevarious types of molded articles by an optional method such asextrusion, injection molding, blow molding, calendar molding, casting,coating, sheeting and lamination.

A production method of molded articles of the thermoplastic resincomposition (C) is not especially limited; molding may be carried outafter the thermoplastic resin composition is fabricated in advance, orthe thermoplastic resin composition (C) can also be producedsimultaneously when molding is carried out (for example, a side feedsystem and a dry blend system). The side feed system is a method inwhich for example, two components are charged from different feeders toan extruder in order to regulate mutual melt states to be blended in a.polymer blend. The dry blend system involves mixing resin materials tobe blended in a pellet form in advance and charging the mixture in thestate in a molding machine (a resin molding machine such as an extruderor an injection molding machine). The thermoplastic resin. composition(C) suffices if holding thermoplasticity in the fabrication time of thecomposition, and after the fabrication, may or may not have thethermoplasticity. There are cases where a final product is a resincomposition having no thermoplasticity, for example, by addition of acrosslinking agent.

Production of Belt

Conveyance belts and transmission belts require bending fatigueresistance, abrasion resistance, heat resistance, durability and thelike as a flat belt, V belt or the like. Belts are usually imparted witha tensile force and used in an elongated state. Belts are used incombination with resin-made or metal-made pulleys rotating at a highspeed, and are contacted with pulleys, cause to be wound round pulleysand to fit thereon, and are exposed to collision with and rubbing onconveyed materials, and the like. The thermoplastic resin composition(C), since being excellent particularly in the bending fatigueresistance, can effectively be used as belts used in layouts in whichthe belts undergo severe bending fatigue, such as layouts in which aplurality of pulleys are combined and layouts having small-diameterpulleys. A too soft belt causes creeping deformation and the like, andreduces the life; and a too hard belt gives a large abrasion amount andthe like, and also reduces the life. Having reasonable flexibility,abrasion resistance and bending fatigue resistance gives a highestperformance to belts. Belts are usually produced in a long shape bylaminating a resin or an elastomer with a fiber, a woven fabric or thelike by a thermoplastic molding machine of extrusion or the like. Thebelts are used as they are in some cases, but usually, are subjected toendless processing and used in the state of having a continuous beltback surface.

The thermoplastic resin composition (C) (thermoplastic elastomer alloyor the like), since being capable of being melt molded or thermallyprocessed, can be produced by utilizing an optional molding method suchas extrusion, injection molding, blow molding, calendering or casting.

FIG. 11 is a schematic perspective diagram illustratively showing oneexample of a method for producing the belt according to the presentinvention. In this example, the thermoplastic resin composition (C)(thermoplastic elastomer alloy or the like) is continuously meltextruded in a sheet form with an extruder 4 from a die (T-die) at theend thereof; while the melt resin 20 (thermoplastic resin) is poured, atthe vicinity of the die, into a cavity formed between the surface of amold roll 5 for molding a belt (flat belt or the like) 1 as an objectand a steel band 9; and core wires 3 (aramid cords, glass cords, steelcords or the like) are drawn in to thereby mold the belt. A press roll6, a roll 7 and a roll 8 are disposed in the vicinity of the moldingmold roll 5; the steel band 9 is stretched between each roll 6 to 8, andis made to turn together in cooperation with the molding mold roll 5.The core wires 3 are embedded in the melt resin by a pressure of themolding mold. roll 5 and the steel band 9 to thereby mold a long-sizedbelt (flat belt or the like) 1.

An endless belt can be manufactured as follows from the long-sized beltthus obtained. That is, the long-sized belt obtained above is cut into anecessary length by a certain-width. finger (W)-shaped blade; both endsof the cut belt are abutted, and set in a mold having a convexo-concaveshape conforming to a belt tooth profile on the surface; and the abuttedportion is fused by hot. press to form a joint to thereby make anendless belt. Here, although the core wires (steel cords or the like)are divided at the cut portions, the resin portions fuse and are unitedto thereby hold a strength necessary as a belt. An endless belt may be aseamless belt having no joint. The seamless belt having no joint makes afurther highly durable belt.

The belt according to the present invention is excellent not only inabrasion resistance but also in bending fatigue resistance, and hardlycauses abrasion, damage, cracks, breakage and the like even if beingcontinuously or intermittently used at a high load for a longtime, andis thus remarkably excellent in durability and has an elongated life.

EXAMPLES

Hereinafter, the present invention will be described more specificallyby way of Examples and Comparative Examples. The present invention isnot any more limited thereto. The average dispersed particle aspectratio and the average dispersed particle diameter of dispersed particlesin a thermoplastic resin composition (thermoplastic elastomer alloy orthe like) were measured by a scanning electron microscope (SEM), atransmission electron microscope (TEN) and an atomic force microscope(AFM).

Materials used in Examples and the like are shown below.

Thermoplastic Resin (A)

-   (1) TPU-1: an adipate-based TPU (thermoplastic polyurethane) of 90    in hardness-   (2) TPU-2: a caprolactone-based TPU (thermoplastic polyurethane) of    90 in hardness-   (3) TPU-3: a PTMG-based TPU (thermoplastic polyurethane) of 92 in    hardness-   (4) TPU-4: an adipate-based TPU (thermoplastic polyurethane) of 92    in hardness-   (5) TPU-5: an adipate-based TPU (thermoplastic polyurethane) of 80    in hardness-   (6) TPEE: trade name “Hytrel 4777” (a thermoplastic polyester    elastomer, made by Du Pont-bray Co., Ltd.)-   (7) TPAE: trade name “UBESTA XPA 9040X1” (a thermoplastic polyamide    elastomer, made by Ube industries, Ltd.)-   (8) POM: trade name “Duracon 1490-44” (a polyacetal resin, made by    Polyplastics Co., Ltd.)-   (9) PEN: trade name “Teonex IN8065S” polyethylene naphthalate resin,    made by Teijin Chemicals Ltd.)

Modified ethylene copolymer (B)

-   (1) MAH-EPDM: trade name “Fusabond N416” (a maleic    anhydride-modified ethylene-propylene-diene copolymerized rubber,    made by Du Pont K. K.)-   (2) X-EA: trade name “Baymac” (an acid-modified ethylene acryl    elastomer, made by Du Pont K. K.)-   (3) MAH-PPM: trade name “Tafmer MP0610” (a maleic anhydride-modified    ethylene-propylene copolymerized rubber, made by Mitsui Chemicals    Inc.)

Ethylene-Propylene-Diene Copolymerized Rubber

EPDM: trade name “EP21” (an ethylene-propylene-diene copolymerizedrubber, made by JSE. Corp.)

Example 1

100 parts by weight of TPU-1 and 10 parts by weight of MAH-EPDM werekneaded using a twin-screw extruder (made by Technovel Corp., trade name“KZW20TW-30”). The extruder was set at a barrel temperature of 200° C.(here, a feeder portion temperature of 160° C.) and a screw rotationfrequency of 300 rpm; and the resins were melt. kneaded, and passedthrough a pelletizer to thereby fabricate a pellet. The obtained pelletwas injection molded using an injection molding machine (made by NisseiPlastic Industrial Co., Ltd., trade name “NEX110-18E”) to therebyfabricate test pieces [100 mm×100 mm×2 mm thick (for abrasion test), 120mm×10 mm×4 mm thick (for Demattja flex test)].

Comparative Example 1

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-1 alone as a rawmaterial resin.

Example 2

A pellet and test pieces were fabricated by the same operation as in.Example 1, except for using 100 parts by weight of TPU-2 and 10 parts byweight of MAH-EPDM as raw material resins.

Comparative Example 2

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-2 alone as a rawmaterial resin.

Example 3

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-3 and 5 parts byweight of MAH-EPDM as raw material resins. An MAH-EPDM particle in anobtained thermoplastic elastomer alloy had an average dispersed particleaspect ratio of 1.23 and an average dispersed particle diameter of 0.35μm.

Example 4

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-3 and 10 parts byweight of MAH-EPDM as raw material resins. An MAH-EPDM particle in anobtained thermoplastic elastomer alloy had an average dispersed particleaspect ratio of 1.11 and an average dispersed particle diameter of 0.42μm.

Example 5

A pellet and test pieces were fabricated by the same operation as in.Example 1, except for using 100 parts by weight of TPU-3 and 20 parts byweight of MAH-EPDM as raw material resins. An MAH-EPDM particle in anobtained thermoplastic elastomer alloy had an average dispersed particleaspect ratio of 1.08 and an average dispersed particle diameter of 0.52μm.

Comparative Example 3

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-3 alone as a rawmaterial resin.

Comparative Example 4

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-3 and 10 parts byweight of EPDM as raw material resins. An EPDM particle in an obtainedthermoplastic elastomer alloy had an average dispersed particle aspectratio of 1.1 and an average dispersed particle diameter of 5.8 μm.

Example 6

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-4 and 5 parts byweight of MAH-EPDM as raw material resins. An MAH-EPDM particle in anobtained thermoplastic elastomer alloy had an average dispersed particleaspect ratio of 1 and an average dispersed particle diameter of 0.62 μm.

Example 7

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-4 and 10 parts byweight of MAH-EPDM as raw material resins. An MAH-EPDM particle in anobtained thermoplastic elastomer alloy had an average dispersed particleaspect ratio of 1.08 and an average dispersed particle diameter of 0.52μm.

Example 8

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-4 and 20 parts byweight of MAH-EPDM as raw material resins. An MAH-EPDM particle in anobtained thermoplastic elastomer alloy had an average dispersed particleaspect ratio of 1.85 and an average dispersed particle diameter of 0.77μm.

Example 9

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-5 and 10 parts byweight of MAH-EPDM as raw material resins.

Comparative Example 5

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-4 alone as a rawmaterial resin.

Comparative Example 6

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-4 and 10 parts byweight of EPDM. as raw material resins. An EPDM particle in an obtainedthermoplastic elastomer alloy had an average dispersed particle aspectratio of 1.1 and an average dispersed particle diameter of 3.2 μm.

Evaluation Test A Taber Abrasion Test

An abrasion loss (mg) after the rotation number of 1,000 times using aTaber abrasion tester using an abrasion wheel H-22 at a load of 9.8 Nwas measured for the test piece of 100 mm×100 mm×2 mm thick, accordingto JIS K7311. The results are shown. in Table 1.

Bending Fatigue Test (Bending Crack-Growing Test)

A Demattia flex test was carried out according to JIS 116260. A notch of0.5 mm in depth was cut across the nearly entire length in the widthdirection of a middle portion of the long side (a position of 60 mm fromthe end in the longitudinal direction) on the strip test piece of 120mm×10 mm×4 mm thick, and the notched test piece was provided for thetest. The test was carried out under the condition of a maximum distancebetween chucks of 80 mm, a motion distance between the chucks of 70 mnand a bending speed of 97 times/min, and a bending number of times(bending fatigue number of times) until the depth of a crack from thenotch of the test piece reached 3.5 mm was measured. The results areshown in Table 1.

Hardness

A hardness was measured according to JIS K6253 (durometer type A). Thepellet was injection molded by an injection molding machine (made byNissei Plastic Industrial Co., Ltd., trade name “NEX110-18E”) to therebyfabricate test pieces of 100 mm×100 mm×2 mm thick; three sheets thereofwere stacked. to thereby prepare a test piece of 6 mm in thickness; anda measurement of a hardness was carried out using the stacked testpiece. The results are shown in Table 1.

Tensile Test

A tensile test was carried out according to JIS K7311, and a breakingstrength (MPA) and a breaking elongation (%) were determined. Theresults are shown in Table 1. Test pieces for the tensile test werefabricated by stamping out the test pieces for the abrasion. test.

Disperse State Checking Test (SEM Observation and AFM Observation))

Cross-sections of the pellets obtained by a twin-screw extruder were cutout by a freezing microtome, and observed using a scanning electronmicroscope (made by Hitachi High-Technologies Corp., trade name“S-4300”) at a magnification of 2,000 times. A SEM photograph of across-section of the pellet obtained in Comparative Example 4 is shownin FIG. 1; a SEM photograph of a cross-section of the pellet obtained inExample 4, in FIG. 2; a SEM photograph of a cross-section of the pelletobtained in Comparative Example 6, in FIG. 3; and a SEM photograph of across-section of the pellet obtained in Example 7, in FIG. 4.Cross-sections of the pellets were further observed using an atomicforce microscope (AFM). An AFM photograph of a cross-section of thepellet obtained in Example 4 is shown in FIG. 9; and an AFM photographof a cross-section of the pellet obtained in Example 7 is shown in FIG.10.

Observation of molded article cross-sections of the thermoplastic resincompositions (thermoplastic elastomer alloys) obtained in the aboveExamples by a scanning electron microscope (SEM) reveals that a modifiedethylene copolymer (modified ethylene-propylene-diene copolymerizedrubber) is highly microdispersed in a matrix comprising a thermoplasticpolyurethane (see FIGS. 2 and 4). For example, according to the SEMphotographs of a magnification of 2,000 times, in a thermoplasticelastomer alloy comprising a modified EPDM and an etheric TPU, althoughunevenness slightly observed, no particle shape cannot be confirmed; andin a thermoplastic elastomer alloy comprising a modified EPDM and anesteric TPU, even almost no unevenness is observed. By contrast, in thecase of using a non-modified EPDM in place of a modified EPDM, particlesof the EPDM are clearly confirmed, and particularly in a thermoplasticelastomer alloy comprising the EPDM and an esteric TPU, it is clearlyobserved that spherical particles of the EPDM are dispersed in a matrixof the esteric TPU. The average particle diameter of the particlesobserved at this time is a value exceeding 3 μm. That the dispersibilityis remarkably improved in the thermoplastic elastomer alloy comprisingthe modified EPDM and the TPU (particularly the esteric TPU) ispresumably because the polarity of modified sites in the modified EPDMhas affinity for polar sites of the TPU.

Further observation of molded article cross-sections of thethermoplastic resin. compositions (thermoplastic elastomer alloys)obtained in the above Examples by using an atomic force microscope (AFM)reveals that particles of the modified EPDM in the matrix (thermoplasticpolyurethane), which are not observed by SEM, are observed and arehighly microdispersed (see FIGS. 9 and 10). According to these AFMphotographs, it is found that the particles are dispersed in an averagedispersed particle diameter of not more than 1 μm in either of thethermoplastic elastomer alloy comprising the modified EPDM and theetheric TPU and the thermoplastic elastomer alloy comprising themodified EPDM and the esteric TPU. Collectively considering theseresults and the above-mentioned results by the SEM photographs, theeffect of the affinity of modified sites for the matrix on thedispersion is clear.

From the evaluation results shown in Table 1, it is clear that themolded articles formed from the thermoplastic resin composition(thermoplastic elastomer alloy) used an the present invention areremarkably better not only in the Taber abrasion loss but also in thebending fatigue resistance than the molded articles formed from athermoplastic resin (thermoplastic polyurethane) alone, and the moldedarticles formed from a thermoplastic elastomer alloy composed of athermoplastic resin (thermoplastic polyurethane) and a non-modifiedethylene-propylene-diene copolymerized rubber. The case where a modifiedethylene-propylene-diene copolymerized rubber added can improve theabrasion resistance and the bending fatigue resistance without spoilingthe material property of a thermoplastic polyurethane. Although even thecase where a non-modified ethylene-propylene-diene copolymerized rubberis added exhibits an improving affect in some degree of the bendingfatigue resistance in some cases, the cases of largely improving theabrasion resistance and the bending fatigue resistance are cases of athermoplastic polyurethane alloyed with a modifiedethylene-propylene-diene copolymerized rubber. From the results of thedisperse state checking test, it is clear that the disperse states arebetter in order of an esteric TPU-EPDM<an etheric TPU-EPDM<an ethericTPU-maleic anhydride-modified EPDM<an esteric TPU-maleicanhydride-modified EPDM. It is further clear from the AFM photographthat any of the thermoplastic elastomer alloys composed of a modifiedEPDM and an. etheric TPU and the thermoplastic elastomer alloys composedof a modified EPDM and an esteric TPU are dispersed in an averagedispersed particle diameter of not more than 1 μm.

The reason why the Taber abrasion and the bending number of times areremarkably improved is conceivably that a retardation effect of crackextension of the component having an energy absorbing effect changesstates from the severe abrasion progress called adhesion wearing of TPUto the mild abrasion progress. This is because the thermoplasticelastomer alloy is obtained as a combination in which a modifiedethylene copolymer component (elastomer component) is near a sphericalshape like a micro phase separation structure, and microdispersed in aTPU. In a simply blended state in no consideration of compatibility andshearing viscosity, the shape of the island (dispersoid) is usuallyirregular and in a mechanically crushed-like shape in many cases, andthen, the adhesive force between the island layer (disperse phase) andthe sea layer (continuous phase) is weak; exfoliation is liable to becaused at the interface when a stress is impressed on molded articles;and the resistance to crack generation also from the island shapebecomes poor. These cause inferior durability in some cases. However,the thermoplastic resin composition, by increasing the adhesive surfaceof the island layer (disperse phase) and the sea layer (continuousphase) and raising the adhesive force, can provide a disperse form inwhich the island. layer (disperse phase) is micro-dispersed and in anearly true spherical shape, and can be remarkably improved in thedurability under the motion. condition impressed with repeated loads,stresses and deformations. Nobody has developed such properties andconfirmed the effects, and the properties and effects have been found byexhaustive devices by the present inventors.

TABLE 1 Comp. Comp. Comp. Example 1 Ex. 1 Example 2 Ex. 2 Example 3Example 4 Example 5 Ex. 3 TPU-1 100 100 TPU-2 100 100 TPU-3 100 100 100100 TPU-4 TPU-5 MAH-EPDM 10 10 5 10 20 (phr) MAH-EPM (phr) EPDM (phr)Taber 9.3 12.9 6.3 11.5 8.1 8.5 8.5 12.5 Abrasion Amount (mg) Bending400,000 5,000 18,000 3,000 8,000 250,000 170,000 3,000 Number Of Times(times) JIS A 90 92 87 88 92 92 90 92 Hardness Breaking — — — — — — — —Strength (MPa) Breaking — — — — — — — — Elongation (%) Aspect Ratio — —— — 1.23 1.11 1.08 — Average — — — — 0.35 0.42 0.52 — Dispersed ParticleDiameter Comp. Comp. Comp. Ex. 4 Example 6 Example 7 Example 8 Ex. 5 Ex.6 Example 9 TPU-1 TPU-2 TPU-3 100 TPU-4 100 100 100 100 100 TPU-5 100MAH-EPDM 5 10 20 10 (phr) MAH-EPM (phr) EPDM (phr) 10 10 Taber 12.4 116.8 10.8 16.4 16.6 7.4 Abrasion Amount (mg) Bending 40,000 15,000330,000 270,000 5,000 17,000 1,800,000 Number Of Times (times) JIS A 9193 93 91 95 91 79 Hardness Breaking — 57 47 38 52 — — Strength (MPa)Breaking — 560 510 490 520 — — Elongation (%) Aspect Ratio 1.1 1 1.081.85 — 1.1 — Average 5.8 0.62 0.52 0.77 — 3.2 — Dispersed ParticleDiameter

Example 10

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPU-4 and 150 partsby weight of MAH-EPDM as raw material resins.

Comparative Example A

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of MAH-EPDM alone as araw material resin.

Example 11 (An Example Using a Polyester-Based Thermoplastic Elastomer)

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPEE and 10 parts byweight of MAH-EPM as raw material resins.

Comparative Example 7

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPEE alone as a rawmaterial resin.

Example 12 (An Example Using a Polyamide-Based Thermoplastic Elastomer)

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPAE and 10 parts byweight of MAH-EPDM as raw material resins.

Comparative Example 8

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of TPAE alone as a rawmaterial resin.

Example 13 (an Example using a Polyacetal Resin)

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of POM and 10 parts byweight of MAH-EPDM as raw material resins.

Comparative Example 9

A pellet and test pieces were fabricated by the same operation as inExample 1, except for using 100 parts by weight of POM alone as a rawmaterial resin.

The above-mentioned evaluation tests were carried out using the testpieces obtained in Examples 10 to 13, Comparative Example A and.Comparative Examples 7 to 9. In Example 11 and Comparative Example 7,the hardnesses were values measured according to JIS K6253 (durometertype D). The results are shown in Table 2.

TABLE 2 Comparative Comparative Comparative Comparative Example 10Example A Example 11 Example 7 Example 12 Example 8 Example 13 Example 9TPU-1 TPU-2 TPU-3 TPU-4 100 TPU-5 TPEE 100 100 TPAE 100 100 POM 100 100MAH-EPDM (phr) 150 100 10 10 MAH-EPM (phr) 10 EPDM (phr) Taber Abrasion— 128 35 67 30.5 39.5 48 62 Amount (mg) Bending Number Of 110,000 52,000— — — — — — Times (times) JIS A Hardness — — — — 94 93 95 95 JIS DHardness — — 47 47 — — — — Breaking Strength — — — — — — — — (MPa)Breaking Elongation — — — — — — — — (%) Aspect Ratio — — — — — — — —Average Dispersed — — — — — — — — Particle Diameter

By using the each evaluation result (bending number of times) ofComparative Example 5 (MAE-EPDM: 0 wt %), Example 7 (MAH-EPDM: 9 wt %),Example 8 (MAH-EPDM: 17 wt %), Example 10 (MAH-EPDM: 60 wt %), andComparative Example A (MAH-EPDM: 100 wt %) obtained in the above, arelationship between the blend ratio (wt %) of a modified ethylenecopolymer (MAH-EPDM) in a thermoplastic resin composition (athermoplastic elastomer alloy) and the bending fatigue resistance isexpressed as a graph (single logarithmic graph) (see FIG. 5). In FIG. 5,the abscissa is the blend ratio (wt) of MAH-EPDM, and the ordinate isthe bending number of times. (a) of FIG. 5 is a graph obtained byplotting data of Comparative Example 5 and Comparative Example A andconnecting these two points by a straight line (broken line). (b) ofFIG. 5 is a graph obtained by plotting data of Comparative Example 5,Example 7, Example 8, Example 10 and Comparative Example A andconnecting the each point by a straight line (solid line). (c) of FIG. 5is a graph obtained by superposing (a) and (b) of FIG. 5.

As shown in FIG. 5, the bending fatigue resistances of the moldedarticles of the resin. compositions in which the modified ethylenecopolymer (B) is dispersed and contained in the thermoplastic resin (A)has more improved values than expected in each single material, andexhibits a synergistic effect.

Examples 14 to 20 and Comparative Examples 10 and 11 (Examples UsingOther Modified Ethylene Copolymers)

100 parts by weight of the total of a polyethylene naphthalate resin(PEN) as a thermoplastic resin and X-EA as a modified ethylene copolymer(the ratio of both the components are shown in Table 3), variableamounts shown in Table 3 of a fatty acid metal salt (magnesiumstearate), a phenol resin and a metal oxide (magnesium oxide) as curingagents, and one part by weight of an antiaging agent(2,2,4-trimethyl-1,2-dihydroquinoline polymer) were added to and kneadedin a Laboplasto Mill (made by Toyo Seki Seisaku-sho, Ltd., trade name“4C150”). First, the resins were sufficiently fused and kneaded, andthereafter the curing agents were added, and after the curing(crosslinking) reaction, the antiaging agent was added. The reaction waschecked by changing behavior of the kneading torque value. The kneadingtemperature was set at 260° C., and the kneading was carried out for atotal of 10 min. Thereafter, test pieces [100 mm×100 mm×2 mm thick (forabrasion test)] were fabricated by press molding. Respective evaluationtest pieces such as tensile test pieces were stamped out from theabrasion test pieces. Bending fatigue test pieces were fabricated byinjection molding. Comparative Example 10 was a PEN resin itself inwhich no additives except for an antiaging agent was added, and a sheetthereof was obtained by injection molding. Comparative Example 11 wasprepared by kneading PEN resin and non-modified EPDM at a temperaturenear the melting point of the PEN by a Laboplasto Mill. Examples 19 and20 were prepared by varying the blend proportion of PEN to X-EA andkneading by a twin-screw extruder in place of the Laboplasto Mill. Theothers were the same as Example 15. Properties of the obtainedthermoplastic resin compositions and the average dispersed particleaspect ratios of the dispersed particles (X-EA particle and the like)were measured and evaluated by the above-mentioned methods. The resultsare shown in Table 3. The tensile elastic modulus, the modulus strengthat 20% elongation, the tensile strength, the tensile elongation rate(tensile elongation) and the tension set were measured by a tensile testaccording to JIS K7311. The hardnesses (Shore A) in Table 3 are valuesmeasured according to JIS K6253 (durometer type A), and the hardnesses(Shore D) therein are values measured according to JIS K6253 (durometertype D).

TABLE 3 Comp. Example Example Example Example Ex. 10 14 15 16 17 BlendPEN 100 45 45 45 45 X-EA — 55 55 55 55 EPDM — — — — — Magnesium Stearate— 1.5 2 3 4 Phenol Resin — 0.75 1 1.5 2 Magnesium Oxide — 0.75 1 1.5 2Dispersion Dispersoid μm — X-EA X-EA X-EA X-EA Average Dispersed — 0.250.25 0.25 0.15 Particle Diameter Aspect ratio — 3.2 2.5 2.5 1.9 PhysicalProperties Tensile Elastic MPa 2200 237 267 210 201 Modulus ModulusStrength at MPa — 12.9 13.7 13.6 13.1 20% Elongation Tensile StrengthMPa 74 23.6 26.8 29.1 29.3 Tensile Elongation % <10 190 200 220 230 RateHardness (Shore A) — 72(A) — — — Hardness (Shore D) 78(D) 45(D) 63(D)63(D) 63(D) Tension set % 100 45 40.5 40.5 41.5 Taber Abrasion Test mg51.9 40.3 40.6 35.6 36.8 Bending Fatigue times — 103,000 252,000 140,000300,000 Number Of Times Example Example Example Comp. 18 19 20 Ex. 11Blend PEN 45 60 40 50 X-EA 55 40 60 — EPDM — — — 50 Magnesium Stearate 92 2 0 Phenol Resin 4.5 1 1 0 Magnesium Oxide 4.5 1 1 0 DispersionDispersoid μm X-EA X-EA X-EA EPDM Average Dispersed 0.15 0.1 0.25 4.1Particle Diameter Aspect ratio 1.6 1.7 3.5 1.9 Physical PropertiesTensile Elastic MPa 266 450 230 228 Modulus Modulus Strength at MPa 16.720.5 11.5 11.1 20% Elongation Tensile Strength MPa 35.5 45.5 42.3 20Tensile Elongation % 230 340 350 210 Rate Hardness (Shore A) — — — —Hardness (Shore D) 66(D) 69(D) 66(D) 57(D) Tension set % 43 47 40 69Taber Abrasion Test mg 39.3 37.8 36.5 54.1 Bending Fatigue times 444,000803,000 180,000 4,250 Number Of Times

A TEM photograph of a sheet cross-section of the resin compositionobtained. in Example 14 is shown in. FIG. 6 [a photograph of amagnification of 10,000 times (in a size of 112 mm×161 mm.)]. A TEM:photograph of a sheet cross-section of the resin composition obtained inExample 19 is shown in FIG. 7 [a photograph of magnification of 10,000times (in a size of 112 mm×161 mm)]. A TEM photograph of a sheetcross-section of the resin composition obtained in Comparative Example11 is shown in FIG. 8 [a photograph of a magnification of 10,000 times(in a size of 112 mm×161 mm)]. It is found that the resin compositionsobtained in Examples 14 and 19 have a very fine disperse state ascompared with. Comparative Example 11.

Example 21

A flat belt was manufactured using the pellet obtained in Example 1[thermoplastic resin composition (thermoplastic elastomer alloy)] (seeFIG. 11). That is, the thermoplastic resin composition (thermoplasticelastomer alloy) is continuously melt extruded in a sheet form from afront end die (T-die) by an extruder 4; while the melt resin(thermoplastic resin composition) 20 is poured, at the vicinity of thedie, into a cavity formed between the surface of a mold roll 5 formolding a flat belt 1 as an object and a steel band 9; and core wires 3(aramid cords, glass cords, steel cords or the like) are drawn in tothereby mold the belt. A press roll 6, a roll 7 and a roll 8 aredisposed in the vicinity of the molding mold roll 5; the steel band 9 isstretched between each roll 6 to 8, and is made to turn together incooperation with the molding mold roll 5. The core wires 3 are embeddedin the melt resin by a pressure of the molding mold roll 5 and the steelband 9 to thereby mold a long-sized flat belt 1.

The obtained long-sized flat belt was cut into a necessary length by acertain-width finger (W)-shaped blade; both ends of the cut belt wereabutted, and set in a mold having a convexo-concave shape conforming toa belt tooth profile on the surface; and the abutted. portion was fusedby hot press to form a joint to thereby obtain an endless belt (beltwidth: 25 mm, belt length: 1,200 mm, belt thickness: 2.5 mm). In theobtained flat belt, the count of the steel cords per 1-inch width is 15.

Comparative Example 12

An endless flat belt was manufactured by the same operation as inExample 21, except for using the pellet (thermoplastic elastomer)obtained in Comparative Example 1.

Evaluation Test B Belt Life Test

The endless flat belts obtained in Example 21 and Comparative Example 12were subjected to a belt life test using an overload running tester. Theconditions of the running test are as follows. The test was finished atthe time point when the belt lost the rotary transmission capability.

Layout: simple two-shafts

Belt size: 30 W×1,000 L

Pulley: φ90

Rotation frequency: 1,500 rpm.

Initial tension: 400 N/30W

As a result, the flat belt of Comparative Example 12 generated damagesuch as cracks at a bending number of times of 9.0×10⁶; by contrast,damage such as cracks was not observed on the flat belt of ComparativeExample 21 even when the bending number of times reached. 1.2×10 ⁸.

From the above results, it is conceivable that the life of the flat belthas a correlation with the abrasion loss in the Taber abrasion test of athermoplastic resin composition (thermoplastic elastomer (alloy)) andthe bending number of times in. the Demattia flex test thereof (Table1).

INDUSTRIAL APPLICABILITY

The belt according to the present invention is excellent not only inabrasion resistance but also in bending fatigue resistance, and hardlycauses abrasion, damage, cracks, breakage and the like on the belt bodyin an early stage and is remarkably excellent in durability, even if thebelt is used at a high load for a long time. Therefore, the belt cansuitably be utilized as belts for power transmission, conveyance and thelike.

Reference Signs List

-   1 BELT-   2 BELT BODY-   3 CORE WIRE-   4 EXTRUDER-   5 MOLDING MOLD ROLL-   6 PRESS ROLL-   7 ROLL-   8 ROLL-   9 STEEL BAND-   20 MELT RESIN (THERMOPLASTIC ELASTOMER ALLOY OR THE LIKE)

1. A belt, excluding toothed belts, being formed from thermoplasticelastomer alloy comprising thermoplastic polyurethane (A11) and amodified ethylene-propylene-diene copolymerized rubber (B1), wherein aweight proportion [(B1)/(A11)] of the modified ethylene-propylene-dienecopolymerized rubber (B1) to the thermoplastic polyurethane (A11) is0.1/99.9 to 30/70.
 2. The belt according to claim 1, wherein themodified ethylene-propylene-diene copolymerized rubber (B1) is anethylene-propylene-diene copolymer modified with maleic anhydride.